JP2020117568A - Anion exchange resin, electrolyte membrane, binder for forming electrode catalyst layer, cell electrode catalyst layer, and fuel cell - Google Patents

Abstract

To provide an anion exchange resin capable of manufacturing an electrolyte membrane excellent in electric characteristics and chemical characteristics, a binder for forming an electrode catalyst layer, and a cell electrode catalyst layer, the electrolyte membrane and the binder for forming the electrode catalyst layer which are formed from the anion exchange resin, the cell electrode catalyst layer formed from the binder for forming the electrode catalyst layer, and a fuel cell having the electrolyte membrane or the cell electrode catalyst layer.SOLUTION: For example, there is provided an anion exchange resin, in which a hydrophobic unit having a bisphenol AF residue being repeated via a carbon-carbon bond and a hydrophilic unit having a hydrophilic group bonded to an anion exchange group via a divalent saturated hydrocarbon group in a fluorene skeleton being repeated via a carbon-carbon bond are bonded via a carbon-carbon bond.SELECTED DRAWING: Figure 1

Description

The present invention relates to an anion exchange resin, an electrolyte membrane, a binder for forming an electrode catalyst layer, a battery electrode catalyst layer and a fuel cell.

Monovalent aromatic ring or divalent hydrocarbon group, divalent silicon-containing group, divalent nitrogen-containing group, divalent phosphorus-containing group, divalent oxygen-containing group, divalent sulfur-containing group , Or a divalent hydrophobic group composed of a plurality of aromatic rings bonded to each other via a carbon-carbon bond and a single aromatic ring, or a divalent hydrocarbon group, a divalent silicon-containing group, 2 A divalent nitrogen-containing group, a divalent phosphorus-containing group, a divalent oxygen-containing group, a divalent sulfur-containing group, or a plurality of aromatic rings bonded to each other via a carbon-carbon bond, and among the aromatic rings At least one is composed of a divalent hydrophilic group having an anion exchange group and a divalent fluorine-containing group having a predetermined structure, and the hydrophobic group has an ether bond, a thioether bond, or a carbon-carbon bond. Hydrophobic unit repeated through, the hydrophilic group has an ether bond, a thioether bond, or a hydrophilic unit repeated through a carbon-carbon bond, the hydrophobic unit and the hydrophilic unit, an ether bond, An ether bond, a thioether bond, or a carbon-silicon bond, which is bonded via a thioether bond or a carbon-carbon bond, and in which the divalent fluorine-containing group is present in the main chain of the hydrophobic unit and/or the hydrophilic unit. Anion exchange resins that are bonded via a bond or a carbon-carbon bond are known (Patent Document 1).

JP, 2016-44224, A

The anion exchange resin described in Patent Document 1 has succeeded in improving electrical characteristics (anion conductivity) while maintaining high chemical characteristics (durability, particularly alkali resistance). Further improvement in electrical characteristics is desired.

The present invention provides an electrolyte membrane having excellent electrical and chemical properties, an anion exchange resin capable of producing a binder for an electrode catalyst layer and a battery electrode catalyst layer, and an electrolyte membrane and an electrode catalyst layer formed from the anion exchange resin. An object of the present invention is to provide a fuel cell comprising a forming binder, a battery electrode catalyst layer formed from the electrode catalyst layer forming binder, and an electrolyte membrane or a battery electrode catalyst layer thereof.

In order to solve the above problems, the anion exchange resin of the present invention,
A divalent hydrophobic group represented by the following formula (1),
Consisting of a single aromatic ring or a divalent hydrocarbon group, a divalent silicon-containing group, a divalent nitrogen-containing group, a divalent phosphorus-containing group, a divalent oxygen-containing group, or a divalent sulfur-containing group. A divalent group consisting of a linking group which is a group, and/or a plurality of aromatic rings bonded to each other via a carbon-carbon bond, wherein at least one of the linking group and the aromatic ring is bonded to an anion exchange group-containing group. Consisting of a hydrophilic group of
A hydrophobic unit consisting of the hydrophobic group alone, or the hydrophobic group is repeated through an ether bond, a thioether bond, or a carbon-carbon bond,
Consisting of the hydrophilic group alone, or the hydrophilic group has a hydrophilic unit which is repeated via an ether bond, a thioether bond, or a carbon-carbon bond,
The hydrophobic unit and the hydrophilic unit are bonded via an ether bond, a thioether bond, or a carbon-carbon bond,
It is characterized by

（式中、Ｘは、互いに同一または相異なって、ハロゲン原子、擬ハロゲン化物、または水素原子を示し、Ｙは、互いに同一または相異なって、酸素含有基、硫黄含有基、または直接結合を示し、Ｚは、互いに同一または相異なって、炭素原子またはケイ素原子を示し、Ｒは、互いに同一または相異なって、芳香族基または直接結合を示し、ｈ、ｈ’、ｈ’’、ｉ、ｉ’、およびｉ’’は、互いに同一または相異なって、０以上の整数を示し、ｈ’’’およびｉ’’’は、１以上の整数を示す。）

(In the formula, X is the same or different from each other and represents a halogen atom, a pseudohalide, or a hydrogen atom, and Y is the same or different from each other and represents an oxygen-containing group, a sulfur-containing group, or a direct bond. , Z are the same or different from each other and represent a carbon atom or a silicon atom, R are the same or different from each other and represent an aromatic group or a direct bond, and h, h′, h″, i, i "And i" are the same or different from each other and represent an integer of 0 or more, and h'" and i'" represent an integer of 1 or more.)

In the anion exchange resin of the present invention, in the above formula (1), Xs are the same or different from each other and represent a halogen atom or a pseudohalide, and Rs are the same or different from each other and represent an aromatic group. Is preferred.

In the anion exchange resin of the present invention, it is more preferable that the divalent hydrophobic group is represented by the following formula (1a).

In the anion exchange resin of the present invention, the divalent hydrophilic group is composed of a single polycyclic compound, or a divalent hydrocarbon group, a divalent silicon-containing group, a divalent nitrogen-containing group, A divalent phosphorus-containing group, a divalent oxygen-containing group, or a divalent sulfur-containing group, a linking group, and/or a plurality of polycyclic compounds bonded to each other via a carbon-carbon bond. It is preferable that at least one of the group and the polycyclic compound is bonded to the anion exchange group via a divalent saturated hydrocarbon group having 2 or more carbon atoms.

In the anion exchange resin of the present invention, it is more preferable that the divalent hydrophilic group is a fluorene residue represented by the following formula (2).

（式中、Ａは、互いに同一または相異なって、陰イオン交換基含有基を示すか、または陰イオン交換基を含有する環状構造を示す。）

(In the formula, A's are the same as or different from each other and each represents an anion-exchange group-containing group, or a cyclic structure containing an anion-exchange group.)

In order to solve the above problems, the electrolyte membrane of the present invention is characterized by containing the above anion exchange resin.

In order to solve the above-mentioned problems, the binder for forming an electrode catalyst layer of the present invention is characterized by containing the above anion exchange resin.

In order to solve the above-mentioned problems, the battery electrode catalyst layer of the present invention is characterized by containing the above-mentioned binder for forming an electrode catalyst layer.

In order to solve the above problems, the fuel cell of the present invention comprises:
An electrolyte membrane containing the above anion exchange resin,
A fuel-side electrode, which is arranged opposite to each other with the electrolyte membrane sandwiched therebetween, to which a hydrogen-containing fuel is supplied, and an oxygen-side electrode to which oxygen or air is supplied,
It is characterized by

In the fuel cell of the present invention, it is preferable that the hydrogen-containing fuel is hydrogen, alcohol, or hydrazines.

In order to solve the above problems, the fuel cell of the present invention comprises:
An electrolyte membrane,
Oppositely arranged with the electrolyte membrane interposed therebetween, a fuel-side electrode to which a hydrogen-containing fuel is supplied, and an oxygen-side electrode to which oxygen or air is supplied,
The fuel-side electrode and/or the oxygen-side electrode includes the above-mentioned cell electrode catalyst layer,
It is characterized by

In the fuel cell of the present invention, it is preferable that the hydrogen-containing fuel is hydrogen, alcohol, or hydrazines.

According to the present invention, an electrolyte membrane having excellent electrical and chemical properties, a binder for forming an electrode catalyst layer, and an anion exchange resin capable of producing a battery electrode catalyst layer, an electrolyte membrane and an electrode formed from the anion exchange resin. A fuel cell including a binder for forming a catalyst layer, a battery electrode catalyst layer formed from the binder for forming an electrode catalyst layer, and an electrolyte membrane or a battery electrode catalyst layer can be provided.

It is a schematic block diagram which shows one Embodiment of the fuel cell of this invention. It is a graph which shows the result of the hydroxide ion electric conductivity with respect to the water content of the sample obtained in the Example and the comparative example.

The anion exchange resin of the present invention comprises a divalent hydrophobic group and a divalent hydrophilic group.

In the anion exchange resin of the present invention, the divalent hydrophobic group has a structure represented by the following formula (1).

（式中、Ｘは、互いに同一または相異なって、ハロゲン原子、擬ハロゲン化物、または水素原子を示し、Ｙは、互いに同一または相異なって、酸素含有基、硫黄含有基、または直接結合を示し、Ｚは、互いに同一または相異なって、炭素原子またはケイ素原子を示し、Ｒは、互いに同一または相異なって、芳香族基または直接結合を示し、ｈ、ｈ’、ｈ’’、ｉ、ｉ’、およびｉ’’は、互いに同一または相異なって、０以上の整数を示し、ｈ’’’およびｉ’’’は、１以上の整数を示す。）

(In the formula, X is the same or different from each other and represents a halogen atom, a pseudohalide, or a hydrogen atom, and Y is the same or different from each other and represents an oxygen-containing group, a sulfur-containing group, or a direct bond. , Z are the same or different from each other and represent a carbon atom or a silicon atom, R are the same or different from each other and represent an aromatic group or a direct bond, and h, h′, h″, i, i "And i" are the same or different from each other and represent an integer of 0 or more, and h'" and i'" represent an integer of 1 or more.)

In the above formula (1), Zs are the same or different and each represents a carbon atom or a silicon atom, preferably a carbon atom.

In the above formula (1), Y are the same or different from each other and represent an oxygen-containing group, a sulfur-containing group, or a direct bond, preferably a direct bond.

In the above formula (1), Xs are the same or different and each represents a halogen atom, a pseudohalide, or a hydrogen atom, preferably a halogen atom or a hydrogen atom, and more preferably a fluorine atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The pseudohalide, trifluoromethyl, -CN, -NC, -OCN, -NCO , -ONC, -SCN, -NCS, -SeCN, -NCSe, -TeCN, -NCTe, is -N ₃ like ..

In the above formula (1), Rs are the same or different from each other and represent an aromatic group or a direct bond, preferably an aromatic group. Examples of the aromatic group include divalent residues in the aromatic ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an indene ring, an azulene ring, a fluorene ring, an anthracene ring, a phenanthrene ring, and the like, a monocyclic or polycyclic compound having 6 to 14 carbon atoms, and an azole, oxole, Heterocyclic compounds such as thiophene, oxazole, thiazole, pyridine and the like can be mentioned. The aromatic ring is preferably a monocyclic aromatic hydrocarbon having 6 to 14 carbon atoms, and more preferably a benzene ring.

The aromatic ring may be optionally substituted with a substituent such as a halogen atom, an alkyl group, an aryl group or a pseudohalide. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The pseudohalide, trifluoromethyl, -CN, -NC, -OCN, -NCO , -ONC, -SCN, -NCS, -SeCN, -NCSe, -TeCN, -NCTe, is -N ₃ like .. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group. And other alkyl groups having 1 to 20 carbon atoms; cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, cyclooctyl groups and other cycloalkyl groups having 1 to 20 carbon atoms. Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, and a fluorenyl group.

In the above formula (1), h, h′, h″, i, i′, and i″ are the same or different from each other and represent an integer of 0 or more, preferably an integer of 0 to 20. , More preferably an integer of 0 to 3, and even more preferably 0 or 1.

In the formula (1), h′″ and i′″ are the same or different from each other and represent an integer of 1 or more, preferably an integer of 1 to 20, more preferably an integer of 1 to 3. And more preferably 1.

Examples of the divalent hydrophobic group having the structure represented by the formula (1) include those having the structure represented by the following formula.

In the anion exchange resin of the present invention, in the formula (1), Xs are the same or different from each other and represent a halogen atom or a pseudohalide, and Rs are the same or different from each other and represent an aromatic group. Is preferred. Particularly preferably, examples of the divalent hydrophobic group having such a structure include those having a structure represented by the following formula (1a) (bisphenol AF residue).

In the anion exchange resin of the present invention, the divalent hydrophilic group is composed of a single aromatic ring, or is a divalent hydrocarbon group, a divalent silicon-containing group, a divalent nitrogen-containing group or a divalent divalent group. A plurality of (two or more, preferably two) aromas that are bonded to each other via a phosphorus-containing group, a divalent oxygen-containing group, or a linking group that is a divalent sulfur-containing group, and/or a carbon-carbon bond. A ring, and at least one of the linking group and the aromatic ring is bonded to the anion-exchange group-containing group.

Examples of the aromatic ring include a benzene ring, a naphthalene ring, an indene ring, an azulene ring, a fluorene ring, an anthracene ring, a phenanthrene ring, and the like, a monocyclic or polycyclic compound having 6 to 14 carbon atoms, and an azole, oxole, Heterocyclic compounds such as thiophene, oxazole, thiazole, pyridine and the like can be mentioned.

The aromatic ring is preferably a monocyclic aromatic hydrocarbon having 6 to 14 carbon atoms, and more preferably a benzene ring.

In addition, the aromatic ring may be optionally substituted with a substituent such as a halogen atom, an alkyl group, an aryl group or a pseudohalide. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The pseudohalide, trifluoromethyl, -CN, -NC, -OCN, -NCO , -ONC, -SCN, -NCS, -SeCN, -NCSe, -TeCN, -NCTe, is -N ₃ like .. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group. And other alkyl groups having 1 to 20 carbon atoms; cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, cyclooctyl groups and other cycloalkyl groups having 1 to 20 carbon atoms. Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, and a fluorenyl group.

When the aromatic ring is substituted with a substituent such as a halogen atom, an alkyl group, an aryl group or a pseudohalide, the number of substituents and the substitution position of the substituent such as a halogen atom, an alkyl group, an aryl group or a pseudohalide. Is appropriately set according to the purpose and use.

As the aromatic ring substituted with a halogen atom, more specifically, for example, a benzene ring substituted with 1 to 4 halogen atoms (for example, a benzene ring substituted with 1 to 4 fluorines, 1 to 4 chlorines). 1 to 4 halogen atoms, such as a benzene ring substituted with, a benzene ring substituted with 1 to 4 bromine, a benzene ring substituted with 1 to 4 iodine, etc., are the same or different. May be used).

Examples of the divalent hydrocarbon group include methylene (—CH ₂ —), ethylene, propylene, i-propylene (—C(CH ₃ ) ₂ —), butylene, i-butylene, sec-butylene, pentylene (pentene). ), i-pentylene, sec-pentylene, hexylene (hexamethylene), 3-methylpentene, heptylene, octylene, 2-ethylhexylene, nonylene, decylene, i-decylene, dodecylene, tetradecylene, hexadecylene, octadecylene and the like carbon. The divalent saturated hydrocarbon group of several 1-20 is mentioned.

Divalent hydrocarbon group, preferably a divalent saturated hydrocarbon group having 1 to 3 carbon atoms, specifically, methylene _(-CH 2 -), ethylene, propylene, i- propylene (-C (CH _{3) 2} -) and the like, more preferably methylene _(-CH 2 -), isopropylene (-C _{(CH 3) 2} -) and the like, especially preferably, i- propylene (-C (CH ₃ ) _2- ).

The divalent hydrocarbon group may be substituted with a monovalent residue in the aromatic ring described above.

In the anion exchange resin of the present invention, preferably, the divalent hydrophilic group is composed of a single polycyclic compound, or is a divalent hydrocarbon group, a divalent silicon-containing group, or a divalent nitrogen-containing group. Group, a divalent phosphorus-containing group, a divalent oxygen-containing group, or a linking group that is a divalent sulfur-containing group, and/or a plurality (two or more, preferably, bound to each other via a carbon-carbon bond. 2) polycyclic compound, and at least one of the linking group or the polycyclic compound is bonded to an anion exchange group via a divalent saturated hydrocarbon group having 2 or more carbon atoms. ..

Examples of the polycyclic compound include a naphthalene ring, an indene ring, an azulene ring, a fluorene ring, an anthracene ring, a phenanthrene ring, a carbazole ring, and an indole ring, and a fluorene ring is preferable.

Examples of the divalent hydrocarbon group include the divalent hydrocarbon groups described above.

The anion-exchange group-containing group may be only an anion-exchange group or an anion-exchange group bonded via a divalent saturated hydrocarbon group.

The anion exchange group-containing group may be bonded to at least one of the linking group or aromatic ring of the divalent hydrophilic residue, may be bonded to a plurality of linking groups or aromatic rings, and It may be bonded to a linking group or an aromatic ring. Further, a plurality of anion exchange groups may be bonded to one linking group or aromatic ring.

The anion exchange group is introduced into the side chain at a hydrophilic group, and is not particularly limited, and it is not particularly limited, and it is a quaternary ammonium group, a tertiary amino group, a secondary amino group, a primary amino group, a phosphine, a phosphazene, and Any known anion exchange group such as a quaternary sulfonium group, a quaternary boronium group, a quaternary phosphonium group, and a guanidinium group can be adopted. From the viewpoint of anion conductivity, a quaternary ammonium group is preferable.

As the anion exchange group, preferably -N ⁺ (CH ₃ ) ₃ can be mentioned, but in addition, those having the following structures can be mentioned. In the structural formulas below, * represents a portion bonded to an aromatic ring containing a substituent.

（図中、Ａｌｋ、Ａｌｋ’、Ａｌｋ’’は、上記したアルキル基を示し、ｉＰｒはｉ−プロピル基を示す。）

(In the figure, Alk, Alk′, and Alk″ represent the above-mentioned alkyl groups, and iPr represents an i-propyl group.)

The number of carbon atoms of the divalent saturated hydrocarbon group that binds the linking group or aromatic ring of the divalent hydrophilic residue and the anion exchange group is preferably 2 or more. The number of carbon atoms of the divalent saturated hydrocarbon group is more preferably an integer of 2 to 20, still more preferably an integer of 3 to 10, and particularly preferably an integer of 4 to 8.

Examples of the divalent saturated hydrocarbon group, preferably methylene (- _(CH 2) -), ethylene (- _{(CH 2)} 2 -), trimethylene (- _{(CH 2)} 3 -), tetramethylene (- ( CH _{2) 4} -), pentamethylene _{(- (CH 2) 5 -} ), hexamethylene _{(- (CH 2) 6 -} ), heptamethylene _{(- (CH 2) 7 -} ), octamethylene (- (CH ₂ ) _8- ) and other linear saturated hydrocarbon groups.

Preferred examples of the divalent hydrophilic group having such a structure include those having a structure represented by the following formula.

（式中、Ｉｏｎは、互いに同一または相異なって、陰イオン交換基含有基を示し、ａは、０以上であって陰イオン交換基含有基が結合可能な数の整数（好ましくは、０または１）を示し、ｎは０以上の整数を示す。）

(In the formula, Ion are the same or different from each other and represent an anion exchange group-containing group, and a is 0 or more and an integer of the number capable of binding to the anion exchange group-containing group (preferably 0 or 1) and n represents an integer of 0 or more.)

Further, preferably, the divalent hydrophilic group having such a structure includes a fluorene residue represented by the following formula (2).

（式中、Ａは、互いに同一または相異なって、陰イオン交換基含有基を示すか、または陰イオン交換基を含有する環状構造を示す。）

(In the formula, A's are the same as or different from each other and each represents an anion-exchange group-containing group, or a cyclic structure containing an anion-exchange group.)

Particularly preferably, examples of the divalent hydrophilic group having such a structure include those represented by the following formula (2a), the following formula (2b), the following formula (2c), or the following formula (2d). ..

In the anion exchange resin of the present invention, the above-mentioned hydrophobic group, or the above-mentioned hydrophobic group, a hydrophobic unit repeated via an ether bond, a thioether bond, or a carbon-carbon bond, and the above-mentioned hydrophilic group. The hydrophilic group is composed of a single group or has the hydrophilic unit which is repeated through an ether bond, a thioether bond, or a carbon-carbon bond. The hydrophobic unit is preferably composed of a hydrophobic group alone, or the hydrophobic group is preferably repeated via a carbon-carbon bond, and the hydrophilic unit is composed of a hydrophilic group alone or a hydrophilic group is composed of a carbon-carbon bond. It is preferably formed repeatedly through a carbon bond.

The unit corresponds to a block of a block copolymer that is generally used.

The hydrophobic unit is preferably a unit formed by binding divalent hydrophobic groups represented by the above formula (1) to each other via a carbon-carbon bond. It may be a unit formed by bonding a plurality of divalent hydrophobic groups represented by the above formula (1) to each other in a random form, a regular form such as alternating, or a block form.

Such a hydrophobic unit is represented by the following formula (3), for example.

（式中、Ｘ、Ｙ、Ｚ、ｈ、ｈ’、ｈ’’、ｈ’’’、ｉ、ｉ’、ｉ’’、およびｉ’’’は、上記式（１）のＸ、Ｙ、Ｚ、ｈ、ｈ’、ｈ’’、ｈ’’’、ｉ、ｉ’、ｉ’’、およびｉ’’’と同異議を示し、ｑは、１〜２００を示す。）

(In the formula, X, Y, Z, h, h′, h″, h′″, i, i′, i″, and i′″ are X, Y, and Z, h, h′, h″, h′″, i, i′, i″, and i′″ have the same objection, and q represents 1 to 200.)

In the above formula (3), q represents, for example, 1 to 200, preferably 1 to 50.

Such a hydrophobic unit is more preferably a unit formed by binding divalent hydrophobic groups represented by the above formula (1a) to each other via a carbon-carbon bond.

Such a hydrophobic unit is particularly preferably represented by the following formula (3a).

（式中、ｑは、１〜２００を示す。）

(In the formula, q represents 1 to 200.)

In the above formula (3a), q represents, for example, 1 to 200, preferably 1 to 50.

The hydrophilic unit is preferably composed of a single aromatic ring, or is a divalent hydrocarbon group, a divalent silicon-containing group, a divalent nitrogen-containing group, a divalent phosphorus-containing group, a divalent oxygen-containing group. , Or a linking group which is a divalent sulfur-containing group, and/or a plurality of aromatic rings bonded to each other via a carbon-carbon bond, and at least one of the linking group or the aromatic ring is an anion exchange group. The unit formed by the bivalent hydrophilic group couple|bonded with the containing group mutually bonding via a carbon-carbon bond is mentioned. The hydrophilic unit is more preferably composed of a singular polycyclic compound, or is a divalent hydrocarbon group, a divalent silicon-containing group, a divalent nitrogen-containing group, a divalent phosphorus-containing group or a divalent phosphorus-containing group. An oxygen-containing group, or a linking group that is a divalent sulfur-containing group, and/or a plurality of polycyclic compounds bonded to each other via a carbon-carbon bond, and at least the linking group or the polycyclic compound. One is a unit formed by bonding divalent hydrophilic groups bonded to an anion exchange group via a divalent saturated hydrocarbon group having 2 or more carbon atoms to each other via a carbon-carbon bond. To be It may be a unit formed by bonding a plurality of divalent hydrophilic groups to each other in a random form, a regular form such as alternating, or a block form.

The hydrophilic unit is particularly preferably a unit formed by binding fluorene residues represented by the above formula (2) to each other via a carbon-carbon bond.

Such a hydrophobic unit is represented by the following formula (4), for example.

（式中、Ａは、上記式（２）のＡと同意義を示し、ｍは、１〜２００を示す。）

(In the formula, A has the same meaning as A in the above formula (2), and m represents 1 to 200.)

In the above formula (4), m represents, for example, 1 to 200, preferably 1 to 50.

As such a hydrophilic unit, particularly preferably, as shown by the following formula (4a), a unit formed by bonding hydrophilic groups represented by the above formula (2a) to each other through a carbon-carbon bond, As represented by the following formula (4b), a unit formed by the hydrophilic groups represented by the above formula (2b) being bonded to each other via a carbon-carbon bond, as represented by the following formula (4c), A unit formed by the hydrophilic groups represented by the above formula (2c) being bonded to each other via a carbon-carbon bond, and a hydrophilic group represented by the above formula (2d) as represented by the following formula (4d). Mention may be made of units formed by the groups being linked together via carbon-carbon bonds.

（式中、ｍは、１〜２００を示す。）

(In the formula, m represents 1 to 200.)

In the above formula (4a), the above formula (4b), the above formula (4c), and the above formula (4d), m represents, for example, 1 to 200, preferably 1 to 50.

In the anion exchange resin of the present invention, the above-mentioned hydrophobic unit and the above-mentioned hydrophilic unit are bonded via an ether bond, a thioether bond, or a carbon-carbon bond. In particular, it is preferable that the above-mentioned hydrophobic unit and the above-mentioned hydrophilic unit are bound via a carbon-carbon bond.

As such an anion exchange resin, preferably, as shown by the following formula (5), the hydrophobic unit represented by the above formula (3) and the hydrophilic unit represented by the above formula (4) are carbon-carbon. Anion exchange resins linked via bonds are mentioned.

（式中、Ｘ、Ｙ、Ｚ、ｈ、ｈ’、ｈ’’、ｈ’’’、ｉ、ｉ’、ｉ’’、ｉ’’’、およびｑは、上記式（３）のＸ、Ｙ、Ｚ、ｈ、ｈ’、ｈ’’、ｈ’’’、ｉ、ｉ’、ｉ’’、ｉ’’’、およびｑと同異議を示し、Ａは、上記式（４）のＡと同意義を示し、ｑおよびｍは配合比あるいは繰り返し数を表し、１〜１００を示し、ｏは、繰り返し数を表し、１〜１００を示す。）

(In the formula, X, Y, Z, h, h′, h″, h′″, i, i′, i″, i′″, and q are X in the formula (3), Y, Z, h, h′, h″, h′″, i, i′, i″, i′″, and q are the same objections, and A is A in the above formula (4). And q and m represent the compounding ratio or the number of repetitions and represent 1 to 100, and o represents the number of repetitions and represent 1 to 100).

As such an anion exchange resin, more preferably, as shown by the following formula (6), the hydrophobic unit represented by the above formula (3a) and the hydrophilic unit represented by the above formula (4) are carbon- Anion exchange resins linked via carbon bonds are mentioned.

（式中、Ａは、上記式（４）のＡと同意義を示し、ｑおよびｍは配合比あるいは繰り返し数を表し、１〜１００を示し、ｏは、繰り返し数を表し、１〜１００を示す。）

(In the formula, A represents the same meaning as A in the above formula (4), q and m represent a compounding ratio or the number of repetitions, represent 1 to 100, and o represents the number of repetitions, 1 to 100 Show.)

As such an anion exchange resin, particularly preferably, as shown by the following formula (7a), a hydrophobic unit represented by the above formula (3a) and a hydrophilic unit represented by the above formula (4a) are carbon-based. An anion exchange resin bonded via a carbon bond, wherein a hydrophobic unit represented by the above formula (3a) and a hydrophilic unit represented by the above formula (4b) are carbon-based as represented by the following formula (7b). An anion exchange resin bonded via a carbon bond, wherein a hydrophobic unit represented by the above formula (3a) and a hydrophilic unit represented by the above formula (4c) are carbon-based as represented by the following formula (7c). An anion exchange resin bonded through a carbon bond, a hydrophobic unit represented by the above formula (3a) and a hydrophilic unit represented by the above formula (4d) are carbon as represented by the following formula (7d). -Anion exchange resins linked via carbon bonds.

（式中、ｑおよびｍは配合比あるいは繰り返し数を表し、１〜１００を示し、ｏは、繰り返し数を表し、１〜１００を示す。）

(In the formula, q and m represent a compounding ratio or the number of repetitions and represent 1 to 100, and o represents the number of repetitions and represent 1 to 100.)

（式中、ｑおよびｍは配合比あるいは繰り返し数を表し、１〜１００を示し、ｏは、繰り返し数を表し、１〜１００を示す。）

(In the formula, q and m represent a compounding ratio or the number of repetitions and represent 1 to 100, and o represents the number of repetitions and represent 1 to 100.)

（式中、ｑおよびｍは配合比あるいは繰り返し数を表し、１〜１００を示し、ｏは、繰り返し数を表し、１〜１００を示す。）

(In the formula, q and m represent a compounding ratio or the number of repetitions and represent 1 to 100, and o represents the number of repetitions and represent 1 to 100.)

（式中、ｑおよびｍは配合比あるいは繰り返し数を表し、１〜１００を示し、ｏは、繰り返し数を表し、１〜１００を示す。）

(In the formula, q and m represent a compounding ratio or the number of repetitions and represent 1 to 100, and o represents the number of repetitions and represent 1 to 100.)

The number average molecular weight of such anion exchange resin is, for example, 10 to 1000 kDa, or preferably 30 to 500 kDa, as described above.

The method for producing the anion exchange resin is not particularly limited, and a known method can be adopted. Preferably, a method by polycondensation reaction is adopted.

When an anion exchange resin is produced by this method, for example, a hydrophobic group-forming monomer is prepared, a hydrophilic group-forming monomer having an anion exchange group precursor functional group is prepared, and a hydrophobic group-forming monomer is prepared. A polymer is synthesized by polymerizing a monomer and a hydrophilic group-forming monomer having an anion exchange group precursor functional group, and an anion exchange resin is prepared by ionizing the anion exchange group precursor functional group in the polymer. It can be manufactured. Alternatively, a monomer for forming a hydrophobic group is prepared, a monomer for forming a hydrophilic group is prepared, and a polymer is synthesized by polymerizing a hydrophobic group forming monomer and a monomer for forming a hydrophilic group. An anion exchange resin can be produced by introducing a substituent having an anion exchange group.

For the polycondensation reaction, a conventionally known general method can be adopted. Preferably, a coupling is used that forms a carbon-carbon bond.

Preferred examples of the hydrophobic group-forming monomer include compounds represented by the following formula (11), which correspond to the above formula (1).

（式中、Ｘ、Ｙ、Ｚ、ｈ、ｈ’、ｈ’’、ｈ’’’、ｉ、ｉ’、ｉ’’、およびｉ’’’は、上記式（１）のＸ、Ｙ、Ｚ、ｈ、ｈ’、ｈ’’、ｈ’’’、ｉ、ｉ’、ｉ’’、およびｉ’’’と同異議を示し、Ｔは、互いに同一または相異なって、ハロゲン原子、擬ハロゲン化物、ボロン酸基、ボロン酸誘導体、または水素原子を示す。）

(In the formula, X, Y, Z, h, h′, h″, h′″, i, i′, i″, and i′″ are X, Y, and Z, h, h′, h″, h′″, i, i′, i″, and i′″ are the same as each other, and T is the same or different from each other and is a halogen atom or a pseudo atom. Indicates a halide, boronic acid group, boronic acid derivative, or hydrogen atom.)

As the monomer for forming a hydrophobic group, a compound represented by the following formula (11a) corresponding to the above formula (1a) is particularly preferable.

（Ｔは、互いに同一または相異なって、ハロゲン原子、擬ハロゲン化物、ボロン酸基、ボロン酸誘導体、または水素原子を示す。）

(Ts are the same or different from each other and represent a halogen atom, a pseudohalide, a boronic acid group, a boronic acid derivative, or a hydrogen atom.)

The hydrophilic group-forming monomer having an anion exchange group precursor functional group is preferably a compound represented by the following formula (12), which corresponds to the above formula (2).

（式中、Ｐｒｅは、互いに同一または相異なって、陰イオン交換基含有基前駆官能基を示すか、または陰イオン交換基前駆官能基を含有する環状構造を示し、Ｔは、互いに同一または相異なって、ハロゲン原子、擬ハロゲン化物、ボロン酸基、ボロン酸誘導体、または水素原子を示す。）

(In the formula, Pre are the same or different from each other and represent an anion exchange group-containing group precursor functional group or a cyclic structure containing an anion exchange group precursor functional group, and T is the same or different from each other. Differently, a halogen atom, a pseudohalide, a boronic acid group, a boronic acid derivative, or a hydrogen atom is shown.)

When polymerizing the hydrophobic group-forming monomer and the hydrophilic group-forming monomer having an anion-exchange group precursor functional group by coupling, the compounding amounts of the first monomer and the second monomer are respectively the anion-exchange obtained. The resin precursor polymer is adjusted to have a desired mixing ratio of the hydrophobic unit and the hydrophilic unit.

In these methods, a hydrophobic group-forming monomer and a hydrophilic group-forming monomer having an anion exchange group precursor functional group are dissolved in a solvent such as N,N-dimethylacetamide or dimethylsulfoxide, and bis( A known method such as a method of polymerizing using cyclooct-1,5-diene)nickel (0) or the like as a catalyst can be adopted.

The reaction temperature in the coupling reaction is, for example, −100 to 300° C., preferably −50 to 200° C., and the reaction time is, for example, 1 to 48 hours, preferably 2 to 5 hours.

By coupling the compound represented by the above formula (11) and the compound represented by the above formula (12), an anion exchange resin precursor polymer represented by the following formula (15) is obtained.

（式中、Ｘ、Ｙ、Ｚ、ｈ、ｈ’、ｈ’’、ｈ’’’、ｉ、ｉ’、ｉ’’、ｉ’’’、およびｑは、上記式（１１）のＸ、Ｙ、Ｚ、ｈ、ｈ’、ｈ’’、ｈ’’’、ｉ、ｉ’、ｉ’’、ｉ’’’、およびｑと同異議を示し、Ｐｒｅは、上記式（１２）のＰｒｅと同意義を示し、ｑおよびｍは配合比あるいは繰り返し数を表し、１〜１００を示し、ｏは、繰り返し数を表し、１〜１００を示す。）

(In the formula, X, Y, Z, h, h′, h″, h′″, i, i′, i″, i′″, and q are X in the formula (11), Y, Z, h, h′, h″, h′″, i, i′, i″, i′″, and q are the same objections, and Pre is Pre of the above formula (12). And q and m represent the compounding ratio or the number of repetitions and represent 1 to 100, and o represents the number of repetitions and represent 1 to 100).

Particularly preferably, the anion exchange resin precursor polymer represented by the following formula (16) is obtained by coupling the compound represented by the formula (11a) with the compound represented by the formula (12).

（式中、Ｐｒｅは、上記式（１２）のＰｒｅと同意義を示し、ｑおよびｍは配合比あるいは繰り返し数を表し、１〜１００を示し、ｏは、繰り返し数を表し、１〜１００を示す。）

(In the formula, Pre has the same meaning as Pre of the above formula (12), q and m represent a compounding ratio or the number of repetitions, 1 to 100, o represents the number of repetitions, 1 to 100 Show.)

Then, in this method, the anion-exchange group precursor functional group is ionized. The ionization method is not particularly limited, and a known method can be adopted.

It is possible to adopt a known method such as a method in which the anion exchange resin precursor polymer is dissolved in a solvent such as N,N-dimethylacetamide or dimethylsulfoxide and ionized with methyl iodide or the like as an alkylating agent. it can.

The reaction temperature in the ionization reaction is, for example, 0 to 100° C., preferably 20 to 80° C., and the reaction time is, for example, 24 to 72 hours, preferably 48 to 72 hours.

By ionizing the anion exchange resin precursor polymer represented by the above formula (15), the anion exchange resin represented by the above formula (5) is obtained. Particularly preferably, the anion exchange resin precursor polymer represented by the above formula (16) is ionized to obtain the anion exchange resin represented by the above formula (6).

The ion exchange group capacity of the anion exchange resin is, for example, 0.1 to 4.0 meq. /G, preferably 0.6 to 3.0 meq. /G.

The ion exchange group capacity can be calculated by the following formula (24).
[Ion exchange group capacity (meq./g)]=introduction amount of anion exchange group per hydrophilic unit×repeating unit of hydrophilic unit×1000/(molecular weight of hydrophobic unit×number of repeating units of hydrophobic unit+molecular weight of hydrophilic unit××) Number of repeating units of hydrophilic unit + molecular weight of ion-exchange group x number of repeating units of hydrophilic unit) (24)
The amount of ion exchange groups introduced is defined as the number of ion exchange groups per unit hydrophilic group. The anion-exchange group introduction amount is the number of moles (mol) of the anion-exchange group introduced into the main chain or side chain of the hydrophilic group.

Further, such an anion exchange resin is composed of a divalent hydrophobic group represented by the above formula (1) and a single aromatic ring, or is a divalent hydrocarbon group or a divalent silicon-containing group. A divalent nitrogen-containing group, a divalent phosphorus-containing group, a divalent oxygen-containing group, or a linking group that is a divalent sulfur-containing group, and/or a plurality of aromas bonded to each other via a carbon-carbon bond. A ring, at least one of the linking group or the aromatic ring is composed of a divalent hydrophilic group bonded to an anion-exchange group-containing group, and is composed of the hydrophobic group alone, or the hydrophobic group. Is composed of a hydrophobic unit repeated through an ether bond, a thioether bond, or a carbon-carbon bond and the hydrophilic group alone, or the hydrophilic group has an ether bond, a thioether bond, or a carbon-carbon bond. And a hydrophilic unit which is repeated via the hydrophobic unit and the hydrophilic unit are bonded to each other via an ether bond, a thioether bond, or a carbon-carbon bond. Such an anion exchange resin has excellent electrical characteristics (in particular, electrical conductivity).

In particular, when the hydrophilic group has a hydrophilic unit which is repeated through a carbon-carbon bond, it has excellent durability such as alkali resistance because it does not contain an ether bond. More specifically, when the hydrophilic unit contains an ether bond, decomposition by hydroxide ion (OH ⁻ ) may occur as described below, and alkali resistance may not be sufficient.

On the other hand, since the hydrophilic unit of the anion exchange resin having a hydrophilic unit in which the hydrophilic group is repeated through the carbon-carbon bond does not contain an ether bond, decomposition by the above mechanism does not occur, and as a result, As a result, it has excellent durability such as alkali resistance.

The present invention includes an electrolyte layer (electrolyte membrane) obtained by using such an anion exchange resin, and further a fuel cell including the electrolyte layer (electrolyte membrane). That is, the electrolyte membrane of the present invention is preferably a fuel cell electrolyte membrane.

FIG. 1 is a schematic configuration diagram showing an embodiment of a fuel cell of the present invention. In FIG. 1, the fuel cell 1 includes a fuel cell S, and the fuel cell S includes a fuel side electrode 2, an oxygen side electrode 3 and an electrolyte membrane 4, and a fuel side electrode 2 and an oxygen side electrode 3 are provided. However, they are opposed to each other with the electrolyte membrane 4 interposed therebetween.

The above-mentioned anion exchange resin can be used as the electrolyte membrane 4 (that is, the electrolyte membrane 4 contains the above anion exchange resin).

The electrolyte membrane 4 can be reinforced by, for example, a known reinforcing material such as a porous base material, and further, for example, biaxial stretching treatment for controlling molecular orientation, crystallinity, Various treatments such as heat treatment for controlling the residual stress can be performed. Further, a known filler can be added to the electrolyte membrane 4 in order to increase its mechanical strength, and the electrolyte membrane 4 and a reinforcing agent such as a glass non-woven fabric can be combined by pressing.

Further, in the electrolyte membrane 4, various additives that are normally used, for example, a compatibilizing agent for improving compatibility, for example, an antioxidant for preventing resin deterioration, for example, handleability in molding processing as a film. An antistatic agent, a lubricant, or the like for improving the temperature can be appropriately contained within a range that does not affect the processing and performance of the electrolyte membrane 4.

The thickness of the electrolyte membrane 4 is not particularly limited and is appropriately set depending on the purpose and application.

The thickness of the electrolyte membrane 4 is, for example, 1.2 to 350 μm, preferably 5 to 200 μm.

The fuel-side electrode 2 is opposed to and in contact with one surface of the electrolyte membrane 4. The fuel-side electrode 2 includes, for example, a catalyst layer (cell electrode catalyst layer) in which a catalyst is supported on a porous carrier.

The porous carrier is not particularly limited, and examples thereof include water repellent carriers such as carbon.

The electrode catalyst is not particularly limited, and examples thereof include platinum group elements (Ru, Rh, Pd, Os, Ir, Pt), iron group elements (Fe, Co, Ni), etc., in the periodic table Nos. 8 to 10 (IUPAC Periodic). Table of the Elements (version date 19 February 2010). The same shall apply hereinafter. Group elements of the periodic table such as Cu, Ag, Au, etc., and combinations thereof, and the like are preferable. , Pt (platinum).

For the fuel electrode 2, for example, the porous simple substance and the catalyst are dispersed in a known electrolyte solution to prepare an electrode ink. Then, if necessary, the viscosity of the electrode ink is adjusted by blending an appropriate amount of an organic solvent such as alcohols, and then the electrode ink is subjected to a known method (for example, a spray method, a die coater method, etc.) to form an electrolyte membrane. 4 is applied to one surface and dried at a predetermined temperature to be bonded to one surface of the electrolyte membrane 4 as a thin film electrode film.

Loading amount of the electrode catalyst in the fuel-side electrode 2 is not particularly limited, for example, 0.1 to 10.0 mg / cm ^2, preferably from 0.5 to 5.0 / cm ^2.

In the fuel-side electrode 2, as will be described later, the supplied fuel and the hydroxide ions (OH ⁻ ) that have passed through the electrolyte membrane 4 are reacted to generate electrons (e ⁻ ) and water (H ₂ O). To generate. Note that, for example, when the fuel is hydrogen (H ₂ ), only electrons (e ⁻ ) and water (H ₂ O) are generated, and when the fuel is alcohol, electrons (e ⁻ ) and water are generated. (H ₂ O), carbon dioxide (CO ₂ ) and the like, and when the fuel is hydrazine (NH ₂ NH ₂ ), electrons (e ⁻ ), water (H ₂ O) and nitrogen (N ₂ ) ) Is generated.

The oxygen-side electrode 3 is opposed to and in contact with the other surface of the electrolyte membrane 4. The oxygen-side electrode 3 includes, for example, a catalyst layer (battery electrode catalyst layer) in which a catalyst is supported on a porous carrier.

For the oxygen-side electrode 3, for example, the porous simple substance and the catalyst are dispersed in a known electrolyte solution to prepare an electrode ink. Then, if necessary, the viscosity of the electrode ink is adjusted by blending an appropriate amount of an organic solvent such as alcohols, and then the electrode ink is subjected to an electrolyte membrane by a known method (for example, a spray method, a die coater method, etc.). 4 is applied to the other surface and dried at a predetermined temperature to be bonded to the other surface of the electrolyte membrane 4 as a thin electrode film.

As a result, in the electrolyte membrane 4, the fuel-side electrode 2, and the oxygen-side electrode 3, the thin-film fuel-side electrode 2 is bonded to one surface of the electrolyte membrane 4, and the thin-film oxygen-side electrode 3 is joined to the other surface of the electrolyte membrane 4. To form a membrane/electrode assembly.

Amount of catalyst supported in the oxygen-side electrode 3 is not particularly limited, for example, 0.1 to 10.0 mg / cm ^2, preferably from 0.5 to 5.0 / cm ^2.

In the oxygen-side electrode 3, as will be described later, the supplied oxygen (O ₂ ) reacts with water (H ₂ O) that has passed through the electrolyte membrane 4 and electrons (e ⁻ ) that have passed through the external circuit 13. Generate hydroxide ion (OH ⁻ ).

The fuel cell S further includes a fuel supply member 5 and an oxygen supply member 6. The fuel supply member 5 is made of a gas impermeable conductive member, and one surface of the fuel supply member 5 is in contact with the fuel side electrode 2 so as to face it. The fuel supply member 5 is provided with a fuel-side flow path 7 for contacting the fuel with the entire fuel-side electrode 2 as a zigzag groove recessed from one surface. A supply port 8 and a discharge port 9 penetrating the fuel supply member 5 are continuously formed at the upstream side end and the downstream side end of the fuel side flow passage 7, respectively.

Similarly to the fuel supply member 5, the oxygen supply member 6 is also made of a gas-impermeable conductive member, and one surface of the oxygen supply member 6 is in contact with the oxygen-side electrode 3 so as to face it. The oxygen supply member 6 is also provided with an oxygen-side flow path 10 for bringing oxygen (air) into contact with the entire oxygen-side electrode 3 as a groove having a dented shape that is recessed from one surface. It should be noted that the oxygen-side flow passage 10 also has a supply port 11 and a discharge port 12 that penetrate the oxygen supply member 6 continuously formed at the upstream end and the downstream end thereof, respectively.

The fuel cell 1 is actually formed as a stack structure in which a plurality of the fuel cells S described above are stacked. Therefore, the fuel supply member 5 and the oxygen supply member 6 are actually configured as a separator in which the fuel side channel 7 and the oxygen side channel 10 are formed on both surfaces.

Although not shown, the fuel cell 1 is provided with a current collector plate made of a conductive material, and the electromotive force generated in the fuel cell 1 is taken out from a terminal provided on the current collector plate. Is configured to be able to.

Further, in FIG. 1, the fuel supply member 5 and the oxygen supply member 6 of the fuel cell S are connected by an external circuit 13, and a voltage meter 14 is interposed in the external circuit 13 to measure the generated voltage. I am trying.

In the fuel cell 1, the fuel is supplied to the fuel-side electrode 2 either directly without reforming or after reforming.

Examples of the fuel include hydrogen-containing fuel.

The hydrogen-containing fuel is a fuel containing a hydrogen atom in its molecule, and examples thereof include hydrogen gas, alcohols, hydrazines, and the like, with hydrogen gas or hydrazines being preferable.

Specific examples of hydrazines include hydrazine (NH ₂ NH ₂ ), hydrazine hydrate (NH ₂ NH ₂ ·H ₂ O), hydrazine carbonate ((NH ₂ NH ₂ ) ₂ CO ₂ ), and hydrazine hydrochloride ( NH ₂ NH ₂ · HCl), hydrazine sulfate _{(NH 2 NH 2 · H 2} SO 4), monomethyl hydrazine _(CH 3 NHNH _2), dimethylhydrazine _{((CH 3) 2 NNH 2} , CH 3 NHNHCH 3), a carboxylic hydrazide ((NHNH ₂ ) ₂ CO) and the like. The above-exemplified fuels can be used alone or in combination of two or more kinds.

Among the above-mentioned fuel compounds, carbon-free compounds, that is, hydrazine, hydrazine hydrate, hydrazine sulfate, etc., do not generate CO and CO ₂ and do not cause poisoning of the catalyst. Therefore, it is possible to achieve substantially zero emission.

Further, as the above exemplified fuel, the above fuel compound may be used as it is, but the above exemplified fuel compound may be used, for example, in water and/or alcohol (for example, a lower solvent such as methanol, ethanol, propanol, i-propanol and the like). It can be used as a solution such as alcohol). In this case, the concentration of the fuel compound in the solution is, for example, 1 to 90% by mass, preferably 1 to 30% by mass, although it varies depending on the kind of the fuel compound. The solvents exemplified above can be used alone or in combination of two or more kinds.

Further, as the fuel, the above-mentioned fuel compound can be used as a gas (for example, vapor).

If oxygen (air) is supplied to the oxygen side flow passage 10 of the oxygen supply member 6 and the above-mentioned fuel is supplied to the fuel side flow passage 7 of the fuel supply member 5, then in the oxygen side electrode 3, As described above, electrons (e ⁻ ) generated in the fuel side electrode 2 and moving through the external circuit 13 react with water (H ₂ O) generated in the fuel side electrode 2 and oxygen (O ₂ ). Then, a hydroxide ion (OH ⁻ ) is generated. The generated hydroxide ions (OH ⁻ ) move in the electrolyte membrane 4 made of an anion exchange membrane from the oxygen side electrode 3 to the fuel side electrode 2. Then, in the fuel-side electrode 2, the hydroxide ions (OH ⁻ ) that have passed through the electrolyte membrane 4 react with the fuel to generate electrons (e ⁻ ) and water (H ₂ O). The generated electrons (e ⁻ ) are moved from the fuel supply member 5 to the oxygen supply member 6 via the external circuit 13 and are supplied to the oxygen-side electrode 3. The generated water (H ₂ O) moves in the electrolyte membrane 4 from the fuel side electrode 2 to the oxygen side electrode 3. By such an electrochemical reaction in the fuel side electrode 2 and the oxygen side electrode 3, electromotive force is generated and power generation is performed.

The operating conditions of the fuel cell 1 are not particularly limited, but for example, the pressure on the fuel side electrode 2 side is 200 kPa or less, preferably 100 kPa or less, and the pressure on the oxygen side electrode 3 side is 200 kPa or less, It is preferably 100 kPa or less, and the temperature of the fuel cell S is set to 0 to 120°C, preferably 20 to 80°C.

In such a fuel cell 1, the electrolyte membrane 4 is an electrolyte membrane containing an anion exchange resin having excellent durability.

Therefore, the electrolyte membrane of the present invention obtained by using the anion exchange resin of the present invention, and the fuel cell provided with such an electrolyte membrane have excellent durability.

The present invention also includes a binder for forming an electrode catalyst layer containing the above-mentioned anion exchange resin, a battery electrode catalyst layer containing the binder for forming an electrode catalyst layer, and a fuel cell having the battery electrode catalyst layer. There is.

That is, in the fuel cell 1, the anion-exchange resin can be contained in the binder for forming the electrode catalyst layer when the fuel-side electrode 2 and/or the oxygen-side electrode 3 is formed.

As a method of incorporating the anion exchange resin into the binder for forming an electrode catalyst layer, specifically, for example, the anion exchange resin is shredded and dissolved in an appropriate amount of an organic solvent such as alcohol to form an electrode catalyst layer. Prepare a forming binder.

In the binder for forming the electrode catalyst layer, the content ratio of the anion exchange resin is, for example, 2 to 10 parts by mass, preferably 2 to 5 parts by mass with respect to 100 parts by mass of the binder for forming the electrode catalyst layer.

Further, by using the electrode catalyst layer forming binder for forming the catalyst layer (battery electrode catalyst layer) of the fuel side electrode 2 and/or the oxygen side electrode 3 described above, the anion exchange resin is used for the catalyst layer (battery layer). It can be contained in the electrode catalyst layer), whereby a fuel cell 1 including a catalyst layer (cell electrode catalyst layer) containing an anion exchange resin can be obtained.

Then, in such a fuel cell 1, the above-mentioned binder for electrode catalyst layer formation containing an anion exchange resin having excellent durability is used in the formation of the cell electrode catalyst layer.

Therefore, the binder for forming an electrode catalyst layer of the present invention obtained by using the anion exchange resin of the present invention, and the battery electrode catalyst layer obtained by using the binder for forming an electrode catalyst layer have excellent durability. It is possible to secure excellent anion conductivity.

As a result, the fuel cell including such a cell electrode catalyst layer has excellent durability and can secure excellent anion conductivity.

Although the embodiment of the present invention has been described above, the embodiment of the present invention is not limited to this, and the design can be appropriately modified without changing the gist of the present invention.

Applications of the fuel cell of the present invention include, for example, a power source for a drive motor in an automobile, a ship, an aircraft, etc., a power source in a communication terminal such as a mobile phone, and the like.

Next, the present invention will be described based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Example 1: Synthesis of anion exchange resin BAF-QAF (IEC=1.9 meq./g)]
<Synthesis of Monomer 1>
Bisphenol AF (18.0 g, 53.8 mmol) and dichlorotriphenylphosphorane (36.0 g, 107 mmol) were added to a 300 mL round bottom three-necked flask equipped with a nitrogen inlet and a cooling tube, and reacted at 350° C. for 4 hours. I went. Dichloromethane and hexane were added to the reaction mixture, followed by purification by silica gel column chromatography (developing solvent: hexane), followed by vacuum drying (60° C.) overnight to obtain Monomer 1 (white solid) represented by the following formula. Was obtained in a yield of 60%.

<Synthesis of Monomer 2>
Fluorene (83.1 g, 0.50 mol), N-chlorosuccinimide (167 g, 1.25 mol), and acetonitrile (166 mL) were added to a 500 mL round bottom three-necked flask. This mixture was stirred to make a uniform solution, 12M hydrochloric acid (16.6 mL) was added, and the reaction was carried out at room temperature for 24 hours. The precipitate recovered from the reaction solution by filtration was washed with methanol and pure water, and then vacuum dried (60° C.) overnight to obtain Monomer 2 (white solid) represented by the following formula with a yield of 65%. It was

<Synthesis of Monomer 3>
Monomer 2 (8.23 g, 35.0 mmol) and 1,6-dibromohexane (53 mL) were added to a 300 mL round bottom three-necked flask. After stirring this mixture to form a uniform solution, a mixed solution of tetrabutylammonium (2.26 g, 7.00 mmol), potassium hydroxide (35.0 g) and pure water (35 mL) was added, and the mixture was stirred at 80° C. for 1 hour. The reaction was carried out over time. Pure water was added to the reaction solution to stop the reaction. The target substance was extracted from the aqueous layer with dichloromethane, and the combined organic layers were washed with pure water and brine, and then water, dichloromethane and 1,6-dibromohexane were distilled off. The crude product was purified by silica gel column chromatography (developing solvent: dichloromethane/hexane=1/4) and then dried under vacuum (60° C.) overnight to obtain a monomer 3 (pale yellow solid) represented by the following formula. Obtained with a yield of 75%.

<Synthesis of Monomer 4>
Monomer 3 (13.2 g, 23.4 mol) and tetrahydrofuran (117 mL) were added to a 300 mL round bottom three-necked flask. This mixture was stirred to form a uniform solution, 40 wt% dimethylamine aqueous solution (58.6 mL) was added, and the reaction was carried out at room temperature for 24 hours. A saturated aqueous sodium hydrogen carbonate solution was added to the reaction solution to stop the reaction. After removing tetrahydrofuran, hexane was added to extract the target component. After washing the organic layer with brine, water and hexane were distilled off. By vacuum drying overnight at 40° C., a monomer 4 (pale yellow solid) represented by the following formula was obtained with a yield of 75%.

(Polymerization reaction)
In a 100 mL round bottom three necked flask equipped with a nitrogen inlet and a condenser, Monomer 1 (0.703 g, 1.88 mmol), Monomer 4 (0.539 g, 1.10 mmol), 2,2'-bipyridine (1.12 g). , 7.16 mmol) and N,N-dimethylacetamide (7 mL) were added. After stirring this mixture to make a uniform solution, bis(1,5-cyclooctadiene)nickel(0) (1.97 g, 7.16 mmol) was added, and the reaction was carried out at 80° C. for 3 hours. The reaction mixture was added dropwise to a mixed solution of methanol and 12M hydrochloric acid (methanol/12M hydrochloric acid=1/1) to stop the reaction. The precipitate recovered from the mixture by filtration is washed with 12M hydrochloric acid, a 0.2M potassium carbonate aqueous solution, and pure water, and then vacuum dried (60° C.) overnight to obtain an anion exchange resin precursor represented by the following formula. Polymer BAF-AF (yellow solid) was obtained with a yield of 99%.

(Quaternization reaction/film formation/ion exchange)
Anion exchange resin precursor polymer BAF-AF (0.30 g) and N,N-dimethylacetamide (1.7 mL) were added to a 50 mL round bottom three-necked flask. This mixture was stirred to form a uniform solution, methyl iodide (1.5 mL) was added, and the reaction was carried out at 40° C. for 48 hours. N,N-dimethylacetamide (2 mL) was added. The reaction solution was dropped into pure water to stop the reaction. The precipitate recovered from the mixture by filtration was washed with pure water and then vacuum dried (60° C.) overnight to obtain an anion exchange resin precursor polymer BAF-QAF (yellow solid). The obtained BAF-QAF and N,N-dimethylacetamide were added to a 20 mL round bottom three-necked flask. The mixture was stirred to make a uniform solution and then filtered. The filtrate was poured onto a glass plate with a silicone rubber edge and dried on a horizontally adjusted hot plate (40° C.). The film was vacuum dried (60° C.) overnight to obtain a light brown transparent film. Furthermore, after being immersed in a 1 M aqueous potassium hydroxide solution for 48 hours, the counter ion of the ion exchange group (quaternary ammonium group) was changed from methyl sulfate ion to hydroxide ion by washing with degassed pure water. Converted As a result, a film of anion exchange resin BAF-QAF (IEC=1.9 meq./g, hydroxide ion type) represented by the following formula was obtained.

[Example 2: Synthesis of anion exchange resin BAF-QAF (IEC=1.3 meq./g)]
A membrane of an anion exchange resin QPAF-4 (IEC=1.3 meq./g) was prepared by using the monomer 1 and the monomer 4 in the same manner as described above, and changing the charged amount of the reagent as needed. Got

[Example 3: Synthesis of anion exchange resin BAF-QAF (IEC=2.4 meq./g)]
Membrane of anion exchange resin QPAF-4 (IEC=2.4 meq./g) was prepared by using Monomer 1 and Monomer 4 in the same manner as described above, and changing the charged amount of the reagent as necessary. Got

[Comparative Example 1: Synthesis of anion exchange resin QPAF-4 (IEC=1.6 meq./g)]
<Synthesis of Monomer 5>
In a 100 mL round bottom three-necked flask equipped with a nitrogen inlet and a condenser, 1,6-diiodoperfluorohexane (5.54 g, 10.0 mmol), 3-chloroiodobenzene (11.9 g, 50 mmol), N, N-Dimethylsulfoxide (60 mL) was added. After stirring this mixture to make a uniform solution, copper powder (9.53 g, 150 mmol) was added, and the reaction was carried out at 120° C. for 48 hours. The reaction solution was dropped into a 0.1 M nitric acid aqueous solution to stop the reaction. The precipitate collected by filtration from the mixture was washed with methanol and the filtrate was collected. After repeating the same operation, pure water was added to the combined filtrate to collect the precipitated white solid by filtration, which was washed with a mixed solution of pure water and methanol (pure water/methanol=1/1). By vacuum drying (60° C.) overnight, a monomer 5 (white solid) represented by the following formula was obtained with a yield of 84%.

(Polymerization reaction)
In a 100 mL round bottom three-necked flask equipped with a nitrogen inlet and a condenser, monomer 5 (1.52 g, 2.91 mmol), monomer 4 (0.82 g, 1.67 mmol), 2,2'-bipyridine (1.70 g). 10.9 mmol) and N,N-dimethylacetamide (11 mL) were added. This mixture was stirred to form a uniform solution, bis(1,5-cyclooctadiene)nickel(0) (3.00 g, 10.9 mmol) was added, and the mixture was reacted at 80° C. for 3 hours. The reaction mixture was added dropwise to a mixed solution of methanol and 12M hydrochloric acid (methanol/12M hydrochloric acid=1/1) to stop the reaction. The precipitate recovered from the mixture by filtration is washed with 12M hydrochloric acid, a 0.2M potassium carbonate aqueous solution, and pure water, and then vacuum dried (60° C.) overnight to obtain an anion exchange resin precursor represented by the following formula. Polymer PAF-4 (yellow solid) was obtained with a yield of 96%.

(Quaternization reaction/film formation/ion exchange)
Anion exchange resin precursor polymer (1.70 g) and N,N-dimethylacetamide (9.6 mL) were added to a 50 mL round bottom three-necked flask. This mixture was stirred to form a uniform solution, methyl iodide (0.45 mL, 7.22 mmol) was added, and the reaction was carried out at room temperature for 48 hours. The reaction solution containing N,N-dimethylacetamide (10 mL) was filtered. The filtrate was poured onto a glass plate with a silicone rubber edge and dried on a horizontally adjusted hot plate (50° C.). This film was washed in pure water (2 L) and then vacuum dried (60° C.) overnight to obtain a light brown transparent film. Furthermore, after being immersed in a 1 M aqueous potassium hydroxide solution for 48 hours, the counter ion of the ion exchange group (quaternary ammonium group) was changed from iodide ion to hydroxide ion by washing with deaerated pure water. Converted Thus, a membrane of anion exchange resin QPAF-4 (m/n=1/0.60, IEC=1.47 meq./g, hydroxide ion type) represented by the following formula was obtained.

[Comparative Example 2: Synthesis of anion exchange resin QPAF-4 (IEC=0.74 meq./g)]
A film of anion exchange resin QPAF-4 (IEC=0.74 meq./g) was prepared by using the above-mentioned monomer 5 and monomer 4 and changing the charged amount of the reagent as needed in the same manner as above. Got

[Comparative Example 3: Synthesis of anion exchange resin QPAF-4 (IEC=1.0 meq./g)]
A membrane of anion exchange resin QPAF-4 (IEC=1.0 meq./g) was prepared by using the above-mentioned monomer 5 and monomer 4 in the same manner as described above, and changing the charged amount of the reagent as needed. Got

[Comparative Example 4: Synthesis of anion exchange resin QPAF-4 (IEC=2.1 meq./g)]
A membrane of anion exchange resin QPAF-4 (IEC=2.1 meq./g) was prepared by using the above-mentioned monomer 5 and monomer 4 in the same manner as described above, and changing the charged amount of the reagent as necessary. Got

<Conductivity of hydroxide ion>
The hydroxide ion conductivity of the anion exchange resin membranes obtained in Examples and Comparative Examples was measured. Specifically, the anion exchange resin membranes (hydroxide ion type) obtained in Examples and Comparative Examples were cut into a sample having a width of 1 cm and a length of 3 cm, which was used as a measurement sample. The hydroxide ion conductivity when immersed in (°C.) was measured. The hydroxide ion conductivity measurement was carried out by washing the sample taken out from a 1 M aqueous potassium hydroxide solution (80° C.) with degassed pure water, and then using an AC four-terminal method (300 mV, 10-100000 Hz) in water at 30° C. It was carried out in. Solartron 1255B/1287 was used as a measuring device, and a gold wire of φ1 mm was used as a probe. The hydroxide ion conductivity σ (S/cm) was calculated from the inter-probe distance L (1 cm), impedance Z (Ω), and membrane cross-sectional area A (cm ² ) by the following formula.
σ=(L/Z)×1/A

The hydroxide ionic conductivity of the example samples increases with IEC and reaches high values up to 71 mS/cm (Fig. 2). On the other hand, the hydroxide ion conductivity of the comparative sample increases with IEC, but shows the same or lower value in the range where IEC exceeds 1.5.

1 Fuel Cell 2 Fuel Side Electrode 3 Oxygen Side Electrode 4 Electrolyte Membrane S Fuel Cell

Claims (12)

A divalent hydrophobic group represented by the following formula (1),
Consisting of a single aromatic ring or a divalent hydrocarbon group, a divalent silicon-containing group, a divalent nitrogen-containing group, a divalent phosphorus-containing group, a divalent oxygen-containing group, or a divalent sulfur-containing group. A divalent group consisting of a linking group which is a group, and/or a plurality of aromatic rings bonded to each other via a carbon-carbon bond, wherein at least one of the linking group and the aromatic ring is bonded to an anion exchange group-containing group. Consisting of a hydrophilic group of
A hydrophobic unit consisting of the hydrophobic group alone, or the hydrophobic group is repeated through an ether bond, a thioether bond, or a carbon-carbon bond,
Consisting of the hydrophilic group alone, or the hydrophilic group has a hydrophilic unit which is repeated via an ether bond, a thioether bond, or a carbon-carbon bond,
The hydrophobic unit and the hydrophilic unit are bonded via an ether bond, a thioether bond, or a carbon-carbon bond,
Anion exchange resin characterized in that.

(In the formula, X is the same or different from each other and represents a halogen atom, a pseudohalide, or a hydrogen atom, and Y is the same or different from each other and represents an oxygen-containing group, a sulfur-containing group, or a direct bond. , Z are the same or different from each other and represent a carbon atom or a silicon atom, R are the same or different from each other and represent an aromatic group or a direct bond, and h, h′, h″, i, i "And i" are the same or different from each other and represent an integer of 0 or more, and h'" and i'" represent an integer of 1 or more.) In the formula (1), Xs are the same or different from each other and represent a halogen atom or a pseudohalide, and Rs are the same or different from each other and represent an aromatic group.
The anion exchange resin according to claim 1, characterized in that The divalent hydrophobic group is represented by the following formula (1a),
The anion exchange resin according to claim 2, wherein

The divalent hydrophilic group is composed of a single polycyclic compound, or is a divalent hydrocarbon group, a divalent silicon-containing group, a divalent nitrogen-containing group, a divalent phosphorus-containing group, or a divalent phosphorus-containing group. Oxygen-containing group, or a linking group which is a divalent sulfur-containing group, and/or a plurality of polycyclic compounds bonded to each other via a carbon-carbon bond, and among the linking group or the polycyclic compound, At least one is bonded to an anion exchange group via a divalent saturated hydrocarbon group having 2 or more carbon atoms,
The anion exchange resin according to any one of claims 1 to 3, wherein The divalent hydrophilic group is a fluorene residue represented by the following formula (2):
The anion exchange resin according to claim 4, characterized in that

(In the formula, A's are the same as or different from each other and each represents an anion-exchange group-containing group, or a cyclic structure containing an anion-exchange group.) An anion exchange resin according to any one of claims 1 to 5,
An electrolyte membrane characterized by the above. An anion exchange resin according to any one of claims 1 to 5,
A binder for forming an electrode catalyst layer, which is characterized in that: The binder for forming an electrode catalyst layer according to claim 7,
A battery electrode catalyst layer characterized by the above. An electrolyte membrane containing the anion exchange resin according to any one of claims 1 to 5,
A fuel-side electrode, which is arranged opposite to each other with the electrolyte membrane sandwiched therebetween, to which a hydrogen-containing fuel is supplied, and an oxygen-side electrode to which oxygen or air is supplied,
A fuel cell characterized by the above. The hydrogen-containing fuel is hydrogen, alcohol, or hydrazines,
The fuel cell according to claim 9, wherein the fuel cell is a fuel cell. An electrolyte membrane,
The fuel-side electrode, which is arranged to face each other with the electrolyte membrane interposed therebetween, to which the hydrogen-containing fuel is supplied, and the oxygen-side electrode which is supplied with oxygen or air,
The fuel-side electrode and/or the oxygen-side electrode includes the cell electrode catalyst layer according to claim 8.
A fuel cell characterized by the above. The hydrogen-containing fuel is hydrogen, alcohol, or hydrazines,
The fuel cell according to claim 11, wherein the fuel cell is a fuel cell.

Images